Note: Descriptions are shown in the official language in which they were submitted.
CA 0224233l l998-07-06
WO98121148 PCT/JP97/04073
FLOCCULANT COMPOSITIONS AND WATER TREATMENT
METHOD USING THE SAME
Field of the Invention
This invention relates to a new flocculant composition
for use in the purification of raw water. It also relates to
a method of water treatment for removing impurities
dissolved or suspended in raw water.
Background of the Invention
A variety of flocculants are used in the water
treatment for municipal and industrial water as well as a
variety waste water including sewage and waste water
originating from chemical, metallurgical, dyeing, starch
and other industries. Conventionally used for clarifying raw
or waste water by separating suspended matter are inorganic
flocculants such as ferrous sulfate, ferric sulfate,
chlorinated copperas (Fe2(SO, )3 ~ FeCl2), ferrous chloride,
ferric chloride, alums, polymeric aluminum chloride and the
like. Auxiliary flocculants are also used lncluding slaked
lime, activated silica, sodium silicate and bentonite.
JP-B-35012733 discloses the use of titanium chlorid in
the rapid clarification of waste water such as cellulose
pulp-waste liquor and coal dressing-waste water. JP-A-
49007178 discloses a flocculant composition containing
aluminum sulfate and titanium sulfate. JP-A-56126483
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discloses that dissolved phosphates in effluent are removed
as precipitates by adding an aqueous composltion containing
ferrous sulfate, ferric sulfate, aluminum sulfate,
magnesium sulfate and titanyl sulfate. JP-A-59049811
discloses a water processing method using titanium
chloride, ferric chloride, ferric sulfate, aluminum sulfate
and aluminum chloride either alone or ln combination. JP-A-
03213194 discloses that the flock-making efficiency of
dyeing waste water is enhanced by combining an inorganic
flocculant with an alkaline earth metal salt. JP-A-07108105
discloses water-blooming Microcystis and Anabaena cells
growing in closed inland water are aggregated by treating
the water with one or more inorganic salts selected from
the group consisting of polymeric iron sulfate, polymeric
iron chloride, ferric sulfate, ferric chloride, calcium
chloride, magnesium chloride, magnesium sulfate, aluminum
sulfate and aluminum chloride. Mizushori Gijitsu (Water
treatment Technology) 5(12):15, 1964 reports the use of
titanium chloride-base flocculant in the reduction of Fe
contents in river water. It also reports that the iron-
removing efficiency of titanium chloride is maximum in an
acidic pH range between 3.5 and 5.5 but a soluble titanium
compound remains in the supernatant.
Aluminum- and iron-based inorganic flocculants
generally have an optimal flock-making pH range, namely
CA 02242331 1998-07-06
WO 98121148 PCT/JP97104073
neutral range for aluminum salts and acidlc to neutral range
for iron salts. In contrast, titanium salts have two
optimal flock-making pH ranges, one ln acidic side and the
other in alkaline side separated by neutral range within
which the titanium salt exhibits no or little flock-making
function but is hydrolyzed into colloidal products.
Accordingly, when attempting to clarify raw water 1ncluding
suspended clay particles with a titanium salt in the
neutral pH range between 6 and 8, the titanium salt will
hardly make coarse flocks of suspending matter but will
remain in water mainly as a colloidal hydrGlyzate which
increases load to settling and filtering facilities. It is
mainly for this reason that have precluded to date the use
of titanium salts for producing municipal water in which
water processing in the neutral pH range is essential.
A need exists for a titanium-based flocculant
composition and a water processing method which can
eliminate or alleviate various proplems as discussed supra.
Summary of the Invention
As stated before, aluminum- or iron-based flocculants
have an optimal pH in the neutral or nearly neutral region
in flock-making ability, while titanium salts are hardly
capable of making flocks in the neutral pH region and
remains as colloidal hydrolyzate in water. The present
invention has its basis on a discovery that titanium salts
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may function as a flocculant in the neutral pH region when
an amount of a water-soluble alkali or alkaline earth metal
salt is added together with the titanium salt.
In a composition aspect, therefore, the present
invention provides a flocculant composition comprising an
aqueous solution of a mixture of titanyl sulfate or
titanium tetrachloride with a water-soluble, neutral alkal
or alkaline earth metal salt at a titanium to alkali or
alkaline earth metal salt ratio calculated as TiO2 of from
0.25:1 to 0.0002:1, preferably from 0.25:1 to 0.01:1 by
weight.
In a preferred embodiment, said alkali or alkaline
earth metal salt is sodium chloride, sodium sulfate,
potassium chloride, calcium chloride, magnesium chloride or
magnesium sulfate.
In another composition aspect, the present invention
provides a flocculant composition comprising an aqueous
solution of a mixture of titanyl sulfate or titanium
tetrachloride, a water-soluble iron salt and a water-
soluble, neutral alkali or alkaline earth metal salt at a
titanium to iron ratio calculated as TiO2 and Fe2 03 of from
1:1 to 40:1 by weight and a titanium to alkali or alkaline
earth metal salt ratio calculated as TiO2 as defined above.
In a preferred embodiment, said water-soluble iron salt
is ferrous sulfate, ferric sulfate, ferrous chloride,
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WO 98121148 PCT/JP97104073
ferric chloride or polymeric ferric chloride.
In a further composition aspect, the present invention
provides a flocculant composition comprising an aqueous
solution of a mixture of titanyl sulfate or titanium
tetrachloride, a water-soluble zirconium salt and a water-
soluble, neutral alkali or alkaline earth metal salt at a
titanium to zirconium ratio calculated as TiO2 and ZrO2 of
from 1:1 to 40:1 by weight and at a titanium to alkali or
alkaline earth metal salt ratio calculated as TiOz as
defined above.
In a preferred embodiment, said water-soluble zirconium
salt is zirconium dichloride oxide of the formula: ZrOCl2,
zirconium chloride hydroxide oxide of the formula:
ZrO(OH)Cl, or zirconium sulfate.
In a still further composition aspect, the present
invention provides a flocculant composition comprising an
aqueous solution of a mixture of titanyl sulfate or titanium
tetrachloride, a water-soluble aluminum salt and a water-
soluble, neutral alkali or alkaline earth metal salt at a
titanium to aluminum ratio calculated as TiO2 and Al2 ~3 of
from 1:1 to 40:1 by weight and at a titanium to alkali or
alkaline earth metal salt ratio calculated as TiO2 as
defined above.
In a preferred embodiment, said water-soluble aluminum
salt is aluminum chloride, polymeric aluminum chloride or
CA 02242331 1998-07-06
WO98121148 PCT1~97104073
aluminum sulfate.
In the method aspect, the present invention provides a
water clarifying method comprising the steps of : (a) adding
into raw water with stirring an aqueous solution of titanyl
sulfate or titanium tetrachloride and a water-soluble
neutral alkali or alkaline earth metal salt at a titanium
to alkali or alkaline earth metal salt ratio calculated as
TiO2 from 0.25:l to 0.0002:l by weight, preferably from
0.25:1 to 0.0l:l by weight; ~b) allowing suspended matter in
the raw water to aggregate into flocks at a pH from 5.6 to
8.7 ; ~c) allowing the flocks to settle; and (d) separating
the supernatant from the flocks.
In a preferred embodiment, the water-soluble, neutral
alkali or alkaline earth metal is sodium chloride, sodium
sulfate, potassium chloride, calcium chlorlde, magnesium
chloride or magnesium sulfate.
In another embodiment, a water-soluble iron salt such
as ferrous sulfate, ferric sulfate, ferrous chloride,
ferric chloride or polymeric ferric chloride is added to
the raw water in step ~a) at a titanium to iron ratio
calculated as TiO2 and Fe, 03 of from l:l to 4:l by weight.
In a further embodiment, a water-soluble zirconium salt
such as zirconium dichloride oxide of the formula: ZrOCl2,
zirconium chloride hydroxide oxide of the formula: ZrO(OH)Cl
or zirconium sulfate is added to the raw water in step (a)
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WO98/21148 PCT/~97/04073
at a titanium to zirconium ratio calculated as TiO2 and ZrO,
of from l:l to 40:l by weight.
In a still further aspect, a water-soluble aluminum
salt such as aluminum chloride, polymeric aluminum chloride
or aluminum sulfate is added to the raw water in step (a)
at a titanium to aluminum ratio calculated as TiO, and
Al203 of from l:l to 40:1 by weight.
Preferably, the aqueous solution of titanyl sulfate or
titanium tetrachloride is added to the raw water is step (a)
to a titanium concentration calculated as TiO2 from l to
200 mg/L.
Other features and advantages of the present invention
will become apparent as the description proceeds.
Detailed Discussion
Titanyl sulfate has the chemical formula: TiOSO, ~ 2H2O
and occurs as white crystals. Commercially available
tltanyl sulfate generally has the following analysis:
TiO, 25-30 wt.%
Total H2SO, 47-53 wt.%
Unbound H2SO, about l0 wt.%
Unbound H2O about l0 wt.%
Any commercial product having the above analysls may be
used in the present invention to advantage.
Titanium tetrachloride is easily hydrolyzed in water
and, therefore, its aqueous solution contains orthotitanic
CA 02242331 1998-07-06
WO98121148 PCT/~97/04073
acid and hydrogen chloride. The term "aqueous solution of
titanium tetrachloride" as used herein refers to an aqueous
solution contalning such hydrolyzates of titanium
tetrachloride. Commercial products having a titanium
content from 5 to 20 wt.% are available in the market and
may be used in the present invention to advantage.
Both titanyl sulfate and titanium tetrachloride produce
insoluble colloidal particles of TiO2 in water in the
neutral pH region. This precludes titanyl sulfate or
titanium tetrachloride from using in the production of
municipal water in particular wherein it is imperative for
both raw water and product water to have a pH between about
6.0 and about 8Ø However, the titanium salt may function
as a flocculant in the neutral pH region when used in
combination with a certain amount of a water-soluble,
neutral alkali or alkaline earth metal salt such as sodium
chloride, sodium sulfate, potassium chloride, calcium
chloride, magnesium chloride or magnesium sulfate. The
amount of the alkali or alkaline earth metal salt is such
that the ratio of titanium calculated as TiO, to the alkali
or alkaline earth metal salt is between 0.25:1 and 0.0002:
1, preferably between 0.25:1 to 0.01:1 by weight. This
enables the titanium salt having no known physiological
toxicity to be used in the treatment of raw water
particularly for municipal water in place of or in addition
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to conventional aluminum-based or iron-based flocculants
without increasing production cost significantly.
The above combination may further comprise a water
soluble iron salt, a water soluble zirconium slat or a water
soluble aluminum salts. ~xamples thereof include ferrous
sulfate, ferric sulfate, ferrous chloride, ferric chloride,
polymeric ferrlc chloride, zirconium dichloride oxide of the
formula: ZrOCl2, zirconium chloride hydroxide oxide of the
formula: ZrO(OH)Cl, zirconium sulfate, alminum chloride,
polymeric aluminum chloride or aluminum sulfate. The amount
of the iron, zirconium or aluminum salt relative to the
titanium salt is such that the ratio of titanlum calculated
as TiO2 to Fe, zr or Al as Fe2 03 ~ ZrO2 or Al2 03 is between
1:1 and 40:1 by weight. The ratio of titanium as TiO2 to the
alkali or alkaline earth metal salt is the same as before.
In use stock solutions of respective chemicals are
- prepared. Although these stock solutions may be added to raw
water separately or concurrently, it is convenient to
formulate a premix of the stock solutions having known
concentrations and known ratios of respective chemicals.
Then the stock solutions or the premix are added to raw
water with stirring. If necessary, a conventional organic
flocculant may also be added. At least a substantial
portion of suspended matter in the raw water will aggregate
into flocks when the pH of water lies within the range
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1 0
between 5.6 and 8.7 after the addition of the chemicals.
After allowing the flocks to settle below a supernatant
layer, product water may be recovered by separating the
supernatant from the flocks.
The exact amounts of respective chemicals will vary
depending upon the nature and quantity of suspended matter
in raw water and also the quality of raw water and/or
product water including the alkalinity of raw water or the
desired pH range of proudct water. It is preferred in
general that the aqueous solution of titanyl sulfate or
titanium tetrachloride be added to raw water to a
concentration calculated as TiO2 from 1 to 200 mg/L. This
concentration will vary, as stated above, depending upon
the alkalinity of raw water and the desired pH range of the
product water. In case of raw water having an acceptable
alkalinity for municipal water a titanium concentration
- calculated as TiO2 from 1 to 10 mg/L will be sufficient to
aggregate suspended matter within a pH range between 6.0 and
8Ø In case of treating various waste water, higher
titanium concentrations up to 200 mg or more as TiO2/L will
be required depending upon the desired pH range of treated
water.
Example
A series of tests were carried out under the following
conditions throughout the tests.
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WO 98/21148 PCT/JP97/04073
~1) Apparatus:
A jar tester, Model JMD-8 available from Miyamoto Riken
Kogyo equipped with a 500 ml glass beaker, a stirrer with a
pair of flat blade paddles each having a size of 68 mm
length x 17 mm width vertically disposed along the rotating
axis and an Eppendolf micropipette.
(2) Stirring condition:
Rapid stirring at 110 rpm for 10 minutes and then slow
stirring at 40 rpm for 10 minutes followed by a settling
time for 10 minutes.
(4) Temperature:
Room temperature.
(5) Raw water:
An artificial water having a turbidity of 20 and a pH
of 7.0 prepared by suspending elutriated kaolin particles
(Kanto Kagaku) in a mixture of municipal water and pure
water having an alkalinity of 25-30 ppm.
(6) Stock solutions:
Name Concentration, g/L
TiOSO., TM Crystals from Tayca Corporation 150 as TiO2
TiCl., aqueous solution, from Toho Titanium 150 as TiO2
Al2 (S04 )3, Taimei Chemical 100 and 10 as Al2 03
Polymeric aluminum chloride, 100 and 10 as Al2 03
Taimei Chemical
FeCl3, Reagent grade from Kanto Chemical 74 and 15 as Fe2O,
Fe2 (SO~ )3, Reagent grade from Kanto Chemical 60 as Fe2O3
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WO98/21148 PCTl~97/04073
ZrOCl2, Daiichl Rare Elements 104 and 15 as ZrOz
ZrO(OH)Cl, Daiichi Rare Elements 116 as ZrO2
Zr(SO~ )2, Daiichi Rare Elements 96 as ZrO2
CaC12, Reagent grade from Kanto Chemical 150 as CaCl2
MgCl2, Reagent grade from Kanto Chemical 150 as MgCl2
MgSO,, Reagent grade from Kanto Chemical 150 as MgSG,
KCl, Reagent grade from Kanto Chemical 150 as KC1
Na2SO~, Reagent grade from Kanto Chemical 150 as Na2SO~
NaC1, Reagent grade from Kanto Chemical 150 as NaC1
~7) Analysis:
A 200 ml aliquot was taken for testing from the
supernatant after standing for 10 minutes.
Turbidity:
Integrating-sphere turbidimeter Model SEP-DT-501D
~Mitsubishi Chemical) was used.
pH:
Standard colorimetric method for municipal water was
used.
Residual (total) Ti and A1:
An amount of HNO3 was added to the sample to make a 1
solution. After standing for 12 hours, the solution was
tested for residual Ti and Al using ICP luminescence
spectrophotometry.
Dissolved Ti and Al:
The sample was filtered through a 0.5 ~ m PTFE filter
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WO98/21148 PCTI~97/04073
and then the above method was followed to determine
dissolved Ti and A1 in the sample.
Example 1
To 500 ml of raw water were added varying amounts of
TlOSO, and polymeric aluminum chloride at varying ratios
shown in Table 1 and Table 2. Turbidity, pH, dissolved Ti
and Al were determined in each test and the results are
shown in Table 1 and Table 2.
Table 1 Turbidity (degree)
Amount of addition TiO2/A12 03 weight ratio
(mg/L as TiO2) 40 20 5 1.60.3
- - - 1.36.4
~ 1.46.6
- - - 1.99.7
- - - 2.88.1
No flock20 20 4.9No Flock
8 0.4 0.50.8 - -
6 0.7 0.30.4
4 1.9 1.20.1
2 No floc.k No Flock 1.0 - -
Table 2 pH, dissolved Ti and Al (mg/L as metal)
at TiO2/Al2 03 weight ratio of 5
Amount of addition
(mg/L as TiO2) pH Ti Al
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W098/21148 PCT1~97/04073
1 4
8 6.1 0.023 0.011
6 6.30.027 0.014
4 6.60.022 0.015
2 6.80.019 0.025
Table 1 and Table 2 show that when the relative
proportion of titanium and aluminum salts calculated as
TiO2/Al2 03 iS 5, the best results are achieved in terms of
turbidity, pH and dissolved Ti and Al in the supernatant.
Example 2
Example 1 was followed except that TiOSO~ was replaced
with TiCl~. Similar results were obtained as shown in Table
3 below.
Table 3 Turbidity (degree)
Amount of addition TiO2/Al~ 03 weight ratio
(mg/L as TiOz) 40 20 5 1.6 0.3
~ 1.1 6.1
~ 1.1 6.2
~ 1.6 9.0
- - --- 2.5 7.8
No flock 20 20 4.6No Flock
8 0.6 0.5 0.2 - -
6 0.4 0.3 0.2 -- -
4 2.0 1.2 0.1
2 No floc~ No Flock 0.6 - -
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l 5
Example 3
Examples 1 and 2 were followed except that polymeric
aluminum chloride was replaced with FeCl~ at a constant
TiO2/Fe2 03 ratio of 5. Similar results were obtained by the
replacement of aluminum salt with iron salts as shown in
Table 4 below.
Table 4 Turbidity(degree) and pH at TiO2/Fe2O3=5
Amount of addition TiOSO4 TiCl4
(mg/L as TiO2) Turbidity pH Turbidity pH
8 0.6 6.4 0.2 6.3
6 0.5 6.5 0.5 6.5
4 1.4 6.8 1.1 6.6
2 No flock 6.9 No flock 6.9
Example 4
- Example 1 was followed except that polymeric aluminum
chloride was replaced with ZrOCl2 at a TiO2/ZrO2 ratio of
5. The results show that the zirconium salt: is also
effective as an auxiliary flocculant in combination with a
titanium salt as shown in Table 5 below.
Table 5 Turbidity(degree) and pH at TiO2/ZrO2=5
Amount of addition TiOSO~ TiCl~
(mg/L as TiO2) Turbidity pH Turbidity pH
8 2.1 6.4 1.1 6.3
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WO 98/21148 PCT/JP97/04073
l 6
6 14.9 6.5 3.4 6.5
4 No flock 6.7 No flock 6.7
2 No flock 6.9 No flock 6.9
Example 5
The effects of co-addition of MgCl, or CaCl2 to the
binary systems of TiCl~ plus polymeric aluminum chloride
(PAC) ~TiO2/Al, 03 =5), TiCl. plus FeCl3 ~TiO2/Fe2 03 =5) and
TiCl4 plus ZrOCl2 ~TiO2/ZrO2=5) on the turbidity and pH of
the supernatant were studied at verying TiO2/MgCl, and
TiO,/CaCl2 ratios. The results are shown in Table 6 to Table
12. The co-addition of MgCl2 or CaCl2 decreased the
turbidity of supernatant while maintaining the pH between
6.0 to 7Ø
Table 6 TiO2/MgCl2=l
Amount of addition Binary system
(mg/L as TiO2)TiO2/Al2 03TiO2/Fe2 03TiO2/ZrO2
at 5 at 5 at 5
Turbidity pH Turbidity pH Turbidity pH
8 0.2 6.3 0.1 6.2 0.7 6.4
6 0.1 6.5 0.4 6.4 2.1 6.5
4 0.1 6.6 1.9 6.5No flock 6.7
2 0.4 6.9 No flock 6.7No flock 6.9
Table 7 TiO,/MgCl,=0.1
Amount of addition Binary system
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WO98/211~ PCTIJP97/04073
l 7
(mg/L as TiO2) TiO2/Al2 03 TiO2/Fe2 03 TiO2/ZrO2
at 5 at 5 at 5
Turbidity pH Turbidity pH Turbidity pH
8 0.3 6.3 0.3 6.2 0.3 6.2
6 0.1 6.5 0.2 6~4 0.4 6.4
4 0.1 6.6 0.6 6.6 1.3 6.6
2 0.7 6.9 3.7 6.8 No flock 6.8
Table 8 TiO2/MgCl2=0.01
Amount of addition Binary system
(mg/L as TiO2) TiO2/Al2 03 TiO2/Fe2 03 TiO2/ZrO2
at 5 at 5 at 5
Turbidity pH Turbidity pH Turbidity pH
8 0.2 6.4 0.2 6.2 0.5 6.3
6 0.2 6.5 0.3 6.5 0.5 6.5
4 0.1 6.7 0.4 6.6 0.6 6.7
2 0.5 6.9 0.6 6.8 1.2 6.8
Table 9 TiO2/CaCl2=l
Amount of addition Binary system
(mg/L as TiO2) TiO2/Al2 03 TiO2/Fe2 03 TiO2/ZrO2
at 5 at 5 at 5
Turbidity pH Turbidity pH Turbidity pH
8 0.2 6.3 0.2 6.2 0.8 6.4
6 0.3 6.5 0.4 6.4 1.9 6.5
4 0.1 6.6 1.9 6.5 No flock 6.6
2 0.2 6.9No flock 6.7 No flock 6.9
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l 8
Table 10 TiO2/CaCl2=0.1
Amount of addition Binary system
(mg/L as TiO2)TiO2/Al2 03TiO2/Fe2OI TiO2/ZrO2
at 5 at 5 at 5
Turbidity pH Turbidity pH Turbidity pH
8 0.2 6.3 0.3 6.20.4 6.2
6 0.1 6.5 0.3 6.40.5 6.3
4 0.2 6.6 0.5 6.60.g 6.5
2 0.6 6.9 2.7 6.811.7 6.8
Table 11 TiO,/CaCl2=0.01
Amount of addition Binary system
(mg/L as TiO2) TiO2/Al, 03 TiO2jFe2 03 TiO2/ZrO2
at 5 at 5 at 5
Turbidity pH Turbidity pH Turbidity pH
8 0.2 6.3 0.3 6.20.7 6.3
6 0.2 6.5 0.4 6.60.5 6.4
4 0.3 6.6 0.4 6.60.6 6.7
2 0.6 6.9 1.1 6.81.1 6.9
Example 6
Example 5 was followed except that all of the three
chemicals were added as a premix of their respective stock
solutions instead of adding separately but concurrently as
in Example 5. The results are shown in Table 12 and Table
CA 02242331 1998-07-06
WO 98121148 PCT/JP97104073
l 9
13. As shown in the Tables, co-addition of chemicals as a
premix was more effective than the separate addition of
individual chemicals.
Table 12 TiO2/CaCl2=0.1
Amount of addition Binary system
(mg/L as TiO2) TiO2/Al2 03 TiO2/Fe2 03 TiO2/ZrO2
at 5 at 5 at 5
Turbidity pH Turbidity pH Turbidity pH
8 0.1 6.5 0.0 6.3 0.2 6.3
6 0.0 6.6 0.0 6.5 0.2 6.4
4 0.1 6.8 0.2 6.7 0.6 6.7
2 0.4 7.0 2.8 6.9 5.1 6.9
Table 13TiO2/CaCl2=0.01
Amount of additlon Binary system
(mg/L as TiO2) TiO2/Al2 03 TiO2/Fe2 03 TiO2/ZrO2
at 5 at 5 at 5
Turbidity pH Turbidity pH Turbidity pH
8 0.2 6.5 0.0 6.3 0.2 6.3
6 0.0 6.6 0.1 6.5 0.2 6.4
4 0.1 6.8 0.2 6.7 0.4 6.7
2 0.3 7.0 0.5 6.9 0.8 6.9
Example 7
The effects of the order of addition of individual
chemicals on the supernatant turbidity were studied using
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2 0
the binary system of TiCl. plus PAC. In case of separate
addition, rapid stirring at 110 rpm for 5 minutes was
repeated twice when adding the first and second chemicals
sequentially. In case of concurrent addition, the rapid
stirring was extended for 10 minutes. The results are shown
in Table 15. Concurrent addition was more effective than
sequential addition as shown in Table 14.
Table 14Supernatant turbidity
Amount of addition TiO2/Al2 03 at 5
(mg/L as TiO2)1st PAC, 2nd TiCl. Reverse Concurrent
2 3.3 1.2 0.5
4 0.5 0.3 0.2
6 0.3 0.4 0.0
8 0.2 0.8 0.3
11 0.0 0.4 0.0
16 2.0 0.2 No flock
24 No flock No flock No flock
Example 8 (for comparison)
The procedure of Example 1 was followed using TiCl~,
TiOSO~, Al2(SO.)I, PAC, FeCl3 or ZrOCl2 alone at varying
concentrations. The results are shown in Table 15 below.
The titanium salts themselves were not effective as a
flocculant at practical concentrations.
Table 15
CA 02242331 1998-07-06
WO 98121148 PCTlJP97tO4073
Amount of addition Supernatant turbidity
~mg/L as metal oxide) TiC4 TiOSO3 Al2(SO,)3 PAC FeCl3 ZrOCl
1 12.3 6.8 6.0
2 8.3 1.8 1.0
3 8.5 0.6 -
4 - 0.8 0.3 No flock
- - 0.3
6 - 0.3 0.2 No flock
8 3.6 9.6 - 0.80.1 9.0
9 2.6 3.0
1.6 1.5 - 16.40.1 4.0
0.5 0.8 - - 10.0 1.8
0.5 1.7 ~ - ~ 20.0
22 18.8 3.7
Example 9
The effects of co-addition of an alkali or alkaline
earth metal sald and a titanium salt on the turbidity of
supernatant were studied at TiO2/alkali or alkaline earth
metal salt ratio of 1, 0.1 and 0.01. The results are shown
in Table 16-Table 21.
Table 16 TiOSo~, TiO2/co-added salt=1
Amount of addition Turbidity
(mg/L as Tio2) MgCl2 MgSO. Na2SO~ NaCl CaCl2 KCl
No No
8 2 flock 3 13 2 flock
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WO98/21148 PCT/~97/04073
2 2
No No No No
6 flock ditto flock flock flock ditto
4 ditto ditto ditto ditto ditto ditto
2 2 ~ - -
Table 17 TiOSo~, TiO2/co-added salt=0.1
Amount of addition Turbidity
(mg/L as TiO2) MgCl2 MgSO~ Na2SOI NaCl CaCl2 Kcl
8 0.2 2 4 2 0.2 2
No No No
6 0.5 5 flock flock 0.3 flock
No
4 3 flock ditto di~to 5 ditto
No No
2 flock ditto ditto ditto flock ditto
Table 18 TiOSOI, TiO2/co-added salt=0.01
Amount of addition Turbidity
(mg/L as TiO2) MgCl2 MgSOI Na2SO, NaCl CaCl2 Kcl
8 0.1 0.6 2 0.2 3 0.2
No
6 0.3 1.0 flock 2 0.2 0.5
4 0.5 1.5 ditto 4 1.0 3
No
2 1 11 ditto flock1.5 20
Table l9 TiCl~, TiO2/co-added salt=l
Amount of addition Turbidity
(mg/L as TiO2) MgSO~ Na2SO~
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8 1 2
6 5 NO flock
4 No flock ditto
2 ditto ditto
Table 20TiCl,, TiO2/co-added salt=0.1
Amount of addition Turbidity
(mg/L as TiO2) MgSO, Na2SO.
8 0.2 2
6 0.2 No flock
4 2 ditto
Table 21TiCl,, TiO2/co-added salt=0.01
Amount of addition Turbidity
~mg/L as TiO2) MgSO4 Na2 S04
8 0.2 2
6 0.2 No flock
4 1 ditto
2 2 ditto
Example 10
The flock-making property of TiCl,-MgCl2 binary system
was studied at varying TiO2/MgCl2 ratios and at varying pH
levels of supernatant. The amount of TiCl. was kept at a
constant level of 4 mg/L as TiO2. The results are shown in
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Table 22.
Settlingness was evaluated according to the following
schedule.
G: Good; F: Fair; B: Bad
As shown in Table 22, co-addition of MgCl, at a
TiOl/MgCl2 ratio of 0.25 or less achieved satisfactory
results in the neutral pH region in terms of flocculation
time, settlingness, turbidity and residual Ti.
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Table 22 TiCl.-MgCl2 at 4 mg/L as TiO2
Supernatant pH
5.6 6.0 6.5 6.9 7.4 7.9 8.7
TiO2/MgC12 Flocculation time 120 120 - -- - 240 180
~second)
No MgCl2 Settlingness G G B :B B F G
Turbidity 1.0 1.1 20 20 20 2. 6 2.8
Residual Ti 0.35 0.42 2.16 2.27 2.17 1.15 1.19
(mg/L as metal~
TiO2/MgCl Flocculation120 120 900 - - 120 120
-1 time(second)
Settlingness G G B B B G G
Turbidity 1.2 1.1 15. 6 20 20 2.1 1.6
Residual Ti 0.45 0.43 1.72 2.18 2.07 1.11 0.71
(mg/L as metal)
TiO2/MgCl2 Flocculation60 60 120 180 120 60 60
=0.25 time(second)
Settlingness G G G G G G G
Turbidity 1.1 1.1 1.8 2.2 1.1 0.5 0.5
Residual Ti 0.45 0.43 0.85 1.15 0.42 0.23 0.16
(mg/L as metal)
TiO2/MgCl2 Flocculation60 60 120 120 120 60 60
=0.1 time(second)
Settlingness G G G G G G G
Turbidity 1.0 1.1 0.8 1.0 0.7 0.5 0.5
Residual Ti 0.42 0.46 0.32 0.45 0.34 0.21 0.24
(mg/L as metal)
TiO2/MgC12 Flocculation60 60 60 60 60 60 60
=0.01 time(second)
Settlingness G G G G G G G
Turbidity 1.1 1.1 1.0 0.8 0.5 0.3 0.9
Residual Ti 0.41 0.42 0.25 0.30 0.23 0.18 0.3
(mg/L as metal)
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Table 22 Continued TiCl,-MgCl2 at 4 mg/L as TiO2
Supernatant pH
5.6 6.0 6.5 6.g 7.4 7.9 8.7
TiO2/MgCl2 Flocculation 60 60 60 60 60 60 60
=0.004 time(second)
Settlingness G G G G G G G
Turbidity 0.8 0.8 1.0 0.5 0.6 O . S 0.7
Residual Ti 0. 28 0.26 0.39 0.23 0.24 0.21 0.34
(mg/L as metal)
TiO2/MgCl~ Flocculation 60 60 60 60 60 60 60
= 0.002 time(second)
Settlingness G G G G G G G
Turbidity 1.0 1. 2 1.2 0.4 0. 6 0 . 6 0. 4
Residual Ti 0. 44 0. 46 0 . 48 0.18 0.26 0.28 0.27
(mg/L as metal)
TiO2/MgCl~ Flocculation 60 60 60 60 60 60 60
=0.001. time(second)
Settlingness G G G G G G G
Turbidity 1. 2 1.1 1.1 0. 5 0 . 4 0.6 0.8
Residual Ti 0.44 0.38 0.34 0.24 0.24 0.27 0.32
(mg/L as metal)
TiO2/MgCl, Flocculation 60 60 60 60 60 60 60
=0.0002 time(second)
Settlingness G G G G G G G
Turbidity 1.5 1.3 1.2 0.6 0.8 0.8 1.0
Residual Ti 0.54 0.50 0.44 0.23 0.28 0.33 0.42
(mg/L as metal)
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Example 11
Example 10 was followed with respect to TiOSO~-MgC12
binary system. The results are shown in Table 23. As shown
in Table 23, similar results were obtained.
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Table 23 TiOSO~-MgCl2 at 4 mg/L as TiO2
Supernatant pH
5.6 6.1 6.6 6.9 7.3 7.9 8.6
No MgClz Flocculation 60 120 ~ 420
time(second)
Settlingness G F B B B B F
Turbidity 0.4 1.4 20 20 20 20 5.2
Residual Ti 0.16 0.63 2.09 2.16 2.08 1.99 1.41
(mgJL as metal)
TiO2 /MgCl~ Flocculation 60 120 -- - -- -- 300
=1 time(second)
Settlingness G G B B B B F
Turbidity 0. 6 1.1 20 20 20 20 3.8
Residual Ti 0.24 0.39 1.95 1. 98 2.00 1. g7 1.28
~mg/L as metal)
TiO2 /MgCl2 Flocculation 60 60 180 540 180 120 60
=0.25 time(second)
Settlingness G G F F F G G
Turbidity 0.6 0.5 1.9 12.2 1.8 0.9 0. 6
Residual Ti 0.24 0.21 0.90 1.61 0.92 0.38 0.32
(mg/L as metal)
TiO2 /MgCl2 Flocculation 60 60 120 360 120 120 60
=0.1 time(second)
Settlingness G G F G G G G
Turbidity 0.6 0. 5 1.2 5.0 1.2 0.6 0.3
Residual Ti 0.31 0. 25 0.39 1. 44 0.58 0.30 0. 23
(mg/L as metal)
TiO2 /MgCl2 Flocculation 60 60 60 120 60 60 60
=0.01 time(second)
Settlingness G G G G G G G
Turbidity 0. 5 0. 4 0.4 0.4 0.4 0.2 0.2
Residual Ti 0.24 0.21 0.19 0. 20 0.12 0.18 0.13
(mg/L as metal)
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Table 23 Continued TiOSO,-MgC12 at 4 mg/L as TiO2
Supernatant pH
5.6 6.1 6.6 6.9 7.3 7.9 8.6
TiO2 /MgCl~ Flocculation 60 60 60 120 60 60 60
=0.004 time(second)
Settlingness G G G G G G G
Turbidity 0.5 0.4 0.4 0.4 0.4 0.2 0.2
Residual Ti 0.19 0.14 0.14 0.17 0.12 0.11 0.14
(mg/L as metal)
TiO2 /MgCl~ Flocculation 60 60 60 120 60 60 60
=0.002 time(second)
Settlingness G G G G G G G
Turbidity 0.5 0. 4 0. 4 0.3 0.4 0.3 0.2
Residual Ti 0.23 0.20 0.18 0.17 0.19 0.14 0.13
~mg/L as metal)
TiO2 /MgCl2 Flocculation 60 60 60 120 60 60 60
=0.001 time~second)
Settlingness G G F G G G G
Turbidity 0. 5 0.5 0. 4 0.3 0.4 0.4 ~- 5
Residual Ti 0.22 0.24 0. 20 0.14 0.18 0. 22 0.24
~mg/L as metal)
TiO2 /MgCl2 Flocculation 60 60 60 120 60 60 60
=0.0002 time(second)
Settlingness G G F G G G G
Turbidity 0.6 0. 5 0.5 0.5 0.6 0.6 0.6
Residual Ti 0.24 0. 18 0.21 0.17 0.20 0.25 0.26
(mg/L as metal)
